Solid detergent compositions

ABSTRACT

The invention relates to solid detergent compositions comprising an aluminosilicate builder and an anionic surfactant and comprising (n) components (i), n being at least 2, whereby the level of aluminosilicate builder in said components together is at least 5% by weight of the composition and the level of the anionic surfactant in said components together is at least 5% by weight of the composition, and whereby the degree of mixture (M) of the anionic surfactant and the aluminosilicate builder is from 0 to 0.7, as defined in the description.

TECHNICAL FIELDS OF THE INVENTION

The invention relates to solid detergent compositions comprisingaluminosilicate builder and surfactants comprised in two or morecomponents which have an improved cleaning performance, an improveddelivery to the wash and a reduced residue formation on the fabrics.

BACKGROUND TO THE INVENTION

All detergents on the market contain surfactants and builders. One ofthe most commonly used builders in phosphate-free detergents arealumninosilicates. They are inexpensive builders, which have as anadditional benefit that they are easy to process. They are in factuseful process aids because they are very good structurants, binders orcarrier materials for other detergent ingredients. Therefore, mostdetergents comprise a base powder made by spray-drying a slurry ofaluminosilicate and surfactant or by agglomerating aluminosilicate andsurfactant. Furthermore, aluminosilicates are useful as dusting agent,to reduce the stickiness or caking of the product.

A problem encountered with these detergents comprising a builder systemcontaining aluminosilicates, it that they tend to cause fabric residues.These residues contain detergent products which is entrapped in thefabrics and/or are insoluble in water. They are noticeable by theconsumer as spotting on the fabric.

Another problem encountered with, in particular solid, detergents istheir tendency to gel upon contact with water. This leads to poordispensing of the product from the dispensing drawer or from adispensing device, and also to poor dissolution of the product into thewash water. This results in residues in the drawer, dispensing device,washing machine and on the fabrics, which may be noticeable as spots onthe fabric. It has been found that in particular surfactants gel uponcontact with water.

The inventors have now surprisingly found that this problems inparticular arises when the surfactants and the aluminosilicates in thedetergent are in close contact with one another, for example when theyare in the detergent in an intimately mixture. This is for example thecase in most known and used base powders, which are agglomerates orspray-dried powders containing. The inventors have now found that theresidue formation problem but also the gelling problem or dissolution ordispensing problem mainly arises in most known products, when about allthe anionic surfactants and aluminosilicates are intimately mixed withone another. When the degree of intimate mixing is reduced or evenavoided completely, they have found that these problems are reduced oreven solved completely.

Thus, the inventors have found a solution which still allows theincorporation of aluminosilicates and surfactants in detergent, but in adifferent manner: the invention provides thereto detergents comprisingat least two components comprising the surfactants and thealuminosilicate in such a manner that a limited degree of intimatemixing occurs.

The detergents of the invention have a reduced fabric residue, inparticular of insoluble detergent ingredients, gelling, an improveddispensing and dissolution. It has been found that these benefits areobtained by any convention way of introducing detergent to the wash,including by use of a dispensing drawer, a dispensing device or byaddition of the detergent in the washing prior to addition of the washload or addition of the detergent on top of the wash load.

The compositions may comprise an effervescence system to further aid thedispensing or dissolution or foaming.

SUMMARY OF THE INVENTION

The invention provides a detergent composition comprising analuminosilicate builder and an anionic surfactant and comprising (n)components (i), n being at least 2, whereby the level of aluminosilicatebuilder in said components together is at least 5% by weight of thecomposition and the level of the anionic surfactant in said componentstogether is at least 5% by weight of the composition, and whereby thedegree of mixture (M) of the anionic surfactant and the aluminosilicatebuilder is from 0 to 0.7, M beingΣ^(n) _(i=1)√(σ_(l).ζ_(i))σ is the fraction of the anionic surfactant of the composition comprisedin component (i); ζ is the fraction of the aluminosilicate of thecomposition comprised in component (i).

The composition is in particular in granular form, in the form of anextrudate, marumerate or pastille, or in the form of an tablet.

The invention also relates to the use in a detergent composition of atleast two components which comprise together an aluminosilicate at alevel of at least 5% by weight of the composition and an anionicsurfactant at a level of at least 5% by weight of the composition ormixtures thereof, whereby the degree of mixture (M) of the anionicsurfactant and the aluminosilicate builder is from 0 to 0.7 forimprovement of the delivery of the detergent to the washing water, Mbeing as defined above.

The detergent compositions have an improved delivery to the washingwater. This means for the purpose of the invention that the compositionsprovide a reduction of fabric residues, in particular of water-insolubledetergent ingredients such as the aluminosilicate, an improvement of thedispensing of the detergent composition, an improvement in thedissolution of the detergent, a reduction in gelling of the detergentand/or a reduction of lump formation of the detergent on the fabrics andfor bleach-containing compositions, an reduced risk of fabric damage.

DETAILED DESCRIPTION OF THE INVENTION

The detergent composition herein comprise at least two components whichcomprise an anionic surfactant or an aluminosilicate or mixturesthereof, whereby if mixtures of aluminosilicate and the surfactant arepresent in one or more of the components, the degree of mixture M isless than 0.7, as defined by the formula. Thus, each component comprisespart or all of the aluminosilicate, all or part of the anionicsurfactant or mixtures thereof, provided that M is from 0 to 0.7.

The components of the detergent composition of the invention compriseeach at least two ingredients, including the anionic surfactant and/orthe aluminosilicate, which are intimately mixed. This means for thepurpose of the invention that the two or more ingredients the componentare substantially homogeneously divided in the component.

Preferably, a component is such that when it comprises an anionicsurfactant, the level of the anionic surfactant is less than 95%,preferably less than 85% or even less than 80% by weight of thecomponent, whereby it may be preferred that the level of the anionicsurfactant is at least 5%, preferably at least 10% more preferably atleast 20% or even at least 30% or even 35% by weight of the component.

Preferably, a component is such that when it comprises analuminosilicate, the level of the aluminosilicate is less than 95%,preferably less than 85% or even less than 80% by weight of thecomponent, whereby it may be preferred that the level of thealuminosilicate is at least 5%, preferably at least 10% by weight of thecomponent.

It should be understood that the detergent composition herein may alsocomprise additional intimately mixtures which are free of anionicsurfactant and free of aluminosilicate. Also, the detergent compositionmay comprise additional ingredients which are not in an intimate mixturewith another ingredient and thus not comprised in a component of thecomposition, as defined herein. For example, the composition maycomprise a detergent ingredient sprayed onto the components herein ordry-added to the components herein.

The components together comprise the aluminosilicate builder at a levelof least 5% by weight of the composition of and the anionic surfactantat a level of at least 5% by weight of the composition. Preferably, thecomponents comprise the aluminosilicate at a level of at least 7%, ormore preferably at least 10% or even 15% by weight of the composition.Depending on the precise formulation of the composition and theconditions of use, the compositions of the invention can even comprisehigher levels of aluminosilicate, such as more than 20% or even morethan 25%, whilst still providing an improved delivery of the detergentto the wash.

Preferably at least 7% or more preferably at least 10% or even at least12% by weight of the composition of anionic surfactant is present in thecomponents. Depending on the precise formulation of the composition andthe conditions of use, it may be preferred to have levels of anionicsurfactants of 18% by weight of the composition or more.

It may be preferred that the detergent composition comprises additionaldry-added aluminosilicate, in particular to dust the detergentcomponents to reduce the risk of caking and/or to provide whiteness tothe product.

Preferably, M is less than 0.65, or even less than 0.45 or even 0.4 oreven 0.35. It may be preferred that M is 0, and that thus no componentsare present in the detergent composition which comprise bothaluminosilicate and anionic surfactants. Whether this is preferred willfor example depend the levels of aluminosilicate and anionic surfactantin the detergent, on the other ingredients present in the formulationand the amount of components present in the formulation.

The components herein preferably are particles, having a particle sizeof at least 50 microns, preferably the particles have an weight averageparticle size of more than 150 or more than 250 microns or even morethan 350 microns, as measured by sieving the composition on sieves ofdifferent mesh size, and calculating the fraction which remain on thesieve and the fraction which passes through the sieve.

It may be preferred that at least one component is made by aspray-drying process, as known in the art, and at least one component ismade by an agglomeration process, as known in the art.

Preferably, the density of the components is from 250 g/liter to 1500g/liter, more preferably at least one of the components, preferably allof the components, has a density from 400 g/liter to 1200 g/liter, morepreferably from 500 g/liter to 900 g/liter.

A highly preferred additional ingredient of the detergent compositionsherein may be oxygen based bleach, preferably containing an hydrogenperoxide source, preferably a perhydrogen compound and a bleachactivator, described herein after. It has been found that the improvedproduct delivery to the wash results in an improved delivery of thebleach system therein, which reduces the risk of deposition of bleach onthe fabric and the risk of patchy fabric damage.

Another preferred additional ingredient is one or more additionalbuilder materials, such as one or more monomeric, oligomeric orpolymeric carboxylate builders and/or crystalline layered silicatebuilder material, described herein after.

Also, depending on the use of the composition and the specificformulation, the detergent composition may be substantially free ofspecific spray-on nonionic alkoxylated alcohol surfactants, which havebeen found to cause gelling or dispensing or dissolution problems. Itmay then be preferred that the composition comprises other nonionicsurfactants, preferably nonionic surfactants which are solid at roomtemperature. A further advantage can be that the omission of sprayed-onnonionic alkoxylated alcohols allows the reduction or omission ofpowdered materials normally required to dust the detergent particlescontaining these liquid nonionic surfactants, such as finealuminosilicates. This not only reduces the process complexity, butmoreover reduces the degree of mixing or contact of the s andsurfactants.

Furthermore, the inventors have found that in certain embodiments of theinvention it may be beneficial to reduce the degree of mixing betweenthe aluminosilicate and one or more of the organic polymeric compounds,when present, for example flocculation polymers and polycarboxylatepolymers, as described herein. The degree of mixture of thealuminosilicate and one or more of these polymers can be determined bythe formula above, wherein a would indicate the weight fraction of thespecific polymer in a certain component. It has been found that this mayreduce the fabric residue formation on the fabrics, in particular ofwater-insoluble components, such as the aluminosilicate.

It may also be useful that in certain embodiments of the invention, thedegree of mixing between amorphous silicate and an anionic surfactant isreduced, when an amorphous silicate is present, in particular inmixtures containing anionic surfactant which are to be spray-dried, itmay be beneficial to reduce the amount of silicate present, for exampleto levels of less than 3% by weight of the mixture, or even less than2%, or even less than 1% or even 0% by weight of the mixture.

Aluminosilicate

Suitable aluminosilicates herein are zeolites which have the unit cellformula Na_(z)[(AlO₂)_(z)(SiO₂)y]. xH₂O wherein z and y are at least 6;the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5,preferably from 7.5 to 276, more preferably from 10 to 264. Thealuminosilicates are in preferably in hydrated form and are preferablycrystalline, containing from 10% to 28%, more preferably from 18% to 22%water in bound form. However, it may be useful to incorporate overdriedaluminosilicates.

The aluminosilicates can be naturally occurring materials, but arepreferably synthetically derived. Synthetic crystalline aluminosilicateion exchange materials are available under the designations Zeolite A,Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.Zeolite A has the formulaNa₁₂[AlO₂)₁₂(SiO₂)₁₂].xH₂Owherein x is from 20 to 30, especially 27. Zeolite X has the formulaNa₈₆ [(AlO₂)₈₆(SiO₂)₁₀₆]. 276 H₂O.Anionic Surfactant

Any anionic surfactant can be incorporated in the compositions of theinvention. The anionic surfactant herein preferably comprises at least asulphate surfactant and/or a sulphonate surfactant or mixtures thereof.It may be preferred that the anionic surfactant comprises only alkylsulphonate surfactant or optionally combined with fatty acids or soapsalts thereof. Alternatively, it may be preferred that the compositioncomprises only akly sulphate surfactant, but hereby it is preferred thatat least a mid-chain branched alkyl surfactant is present or at leasttwo alkyl surfactants are present.

Depending on the precise formulation of the composition and the usethereof, it may be preferred that the compositions herein comprise aparticulate component, as described above, preferably in the form of aflake of an alkyl sulfate or sulphonate surfactant, preferably an alkylbenzene sulphonate, present at a concentration of from 85% to 95% of theparticle or flake, the balance being an sulfate salt and moisture, theparticle or flake being admixed to the other detergent component(s) oringredients.

Other possible anionic surfactants include the isethionates such as theacyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride,alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆-C₁₄ diesters),N-acyl sarcosinates. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tallow oil.

Anionic Sulphonate Surfactant

The anionic sulphonate surfactants in accordance with the inventioninclude the salts of C₅-C₂₀ linear or branched alkylbenzene sulphonates,alkyl ester sulphonates, C₆-C₂₂ primary or secondary alkane sulphonates,C₆-C₂₄ olefin sulphonates, sulphonated polycarboxylic acids, and anymixtures thereof.

Highly preferred is a C12-C16 linear alkylbenzene sulphonate. Preferredsalts are sodium and potassium salts.

The alkyl ester sulphonated surfactant are also suitable for theinvention, preferably those of formulaR¹—CH(SO₃M)- (A)_(x)—C(O)—OR²wherein R¹ is a C₆-C₂₂ hydrocarbyl, R² is a C₁-C₆ alkyl, A is a C₆-C₂₂alkylene, alkenylene, x is 0 or 1, and M is a cation. The counterion Mis preferably sodium, potassium or ammonium.

The alkyl ester sulphonated surfactant is preferably a α-sulpho alkylester of the formula above, whereby thus x is 0. Preferably, R¹ is analkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x ispreferably 0. R² is preferably ethyl or more preferably methyl.

It can be preferred that the R1 of the ester is derived from unsaturatedfatty acids, with preferably 1, 2 or 3 double bonds. It can also bepreferred that R¹ of the ester is derived from a natural occurring fattyacid, preferably palmic acid or stearic acid or mixtures thereof.

Anionic Alkyl Sulphate Surfactant

The anionic sulphate surfactant herein include the linear and branchedprimary and secondary alkyl sulphates and disulphates, alkylethoxysulphates having an average ethoxylation number of 3 or below,fatty oleoyl glycerol sulphates, alkyl phenol ethylene oxide ethersulphates, the C₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl)glucamine sulphates, and sulphates of alkylpolysaccharides.

Primary alkyl sulphate surfactants are preferably selected from thelinear and branched primary C₁₀-C₁₈ alkyl sulphates, more preferably theC₁₁-C₁₅ linear or branched chain alkyl sulphates, or more preferably theC₁₂-C₁₄ linear chain alkyl sulphates.

Preferred secondary alkyl sulphate surfactant are of the formulaR³—CH(SO₄M)—R⁴wherein R³ is a C₈-C₂₀hydrocycarbyl, R⁴ is a hydrocycarbyl and M is acation.

Alkyl ethoxy sulphate surfactants are preferably selected from the groupconsisting of the C₁₀-C₁₈ alkyl sulphates which have been ethoxylatedwith from 0.5 to 3 moles of ethylene oxide per molecule. Morepreferably, the alkyl ethoxysulphate surfactant is a C₁₁-C₁₈, mostpreferably C₁₁-C₁₅ alkyl sulphate which has been ethoxylated with from0.5 to 3, preferably from 1 to 3, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of thepreferred alkyl sulphate and alkyl ethoxysulphate surfactants. Preferredsalts are sodium and potassium salts.

Mid-Chain Branched Anionic Surfactants

Preferred mid-chain branched primary alkyl sulfate surfactants for useherein are of the formula

These surfactants have a linear primary alkyl sulfate chain backbone(i.e., the longest linear carbon chain which includes the sulfatedcarbon atom) which preferably comprises from 12 to 19 carbon atoms andtheir branched primary alkyl moieties comprise preferably a total of atleast 14 and preferably no more than 20, carbon atoms. In the surfactantsystem comprising more than one of these sulfate surfactants, theaverage total number of carbon atoms for the branched primary alkylmoieties is preferably within the range of from greater than 14.5 toabout 17.5. Thus, the surfactant system preferably comprises at leastone branched primary alkyl sulfate surfactant compound having a longestlinear carbon chain of not less than 12 carbon atoms or not more than 19carbon atoms, and the total number of carbon atoms including branchingmust be at least 14, and further the average total number of carbonatoms for the branched primary alkyl moiety is within the range ofgreater than 14.5 to about 17.5.

R, R¹, and R² are each independently selected from hydrogen and C₁-C₃alkyl group (preferably hydrogen or C₁-C₂ alkyl, more preferablyhydrogen or methyl, and most preferably methyl), provided R, R¹, and R²are not all hydrogen. Further, when z is 1, at least R or R¹ is nothydrogen.

M is hydrogen or a salt forming cation depending upon the method ofsynthesis. w is an integer from 0 to 13; x is an integer from 0 to 13; yis an integer from 0 to 13; z is an integer of at least 1; and w+x+y+zis an integer from 8 to 14.

A preferred mid-chain branched primary alkyl sulfate surfactant is, aC16 total carbon primary alkyl sulfate surfactant having 13 carbon atomsin the backbone and having 1, 2, or 3 branching units (i.e., R, R¹and/or R²) of in total 3 carbon atoms, (whereby thus the total number ofcarbon atoms is at least 16). Preferred branching units can be onepropyl branching unit or three methyl branching units.

Another preferred surfactant are branched primary alkyl sulfates havingthe formula

wherein the total number of carbon atoms, including branching, is from15 to 18, and when more than one of these sulfates is present, theaverage total number of carbon atoms in the branched primary alkylmoieties having the above formula is within the range of greater than14.5 to about 17.5; R¹ and R² are each independently hydrogen or C₁-C₃alkyl; M is a water soluble cation; x is from 0 to 11; y is from 0 to11; z is at least 2; and x+y+z is from 9 to 13; provided R¹ and R² arenot both hydrogen.Dianionic Surfactants

The dianionic surfactants are also useful anionic surfactants for thepresent invention, in particular those of formula

where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl,ether, ester, amine or amide group of chain length C₁ to C₂₈, preferablyC₃ to C₂₄, most preferably C₈ to C₂₀, or hydrogen; A nad B areindependently selected from alkylene, alkenylene, (poly) alkoxylene,hydroxyalkylene, arylalkylene or amido alkylene groups of chain lengthC₁ to C₂₈ preferably C₁ to C₅, most preferably C₁ or C₂, or a covalentbond, and preferably A and B in total contain at least 2 atoms; A, B,and R in total contain from 4 to about 31 carbon atoms; X and Y areanionic groups selected from the group comprising carboxylate, andpreferably sulfate and sulfonate, z is 0 or preferably 1; and M is acationic moiety, preferably a substituted or unsubstituted ammonium ion,or an alkali or alkaline earth metal ion.

The most preferred dianionic surfactant has the formula as above where Ris an alkyl group of chain length from C₁₀ to C₁₈, A and B areindependently C₁ or C₂, both X and Y are sulfate groups, and M is apotassium, ammonium, or a sodium ion.

Preferred dianionic surfactants herein include:

-   -   (a) 3 disulphate compounds, preferably 1,3 C7-C23 (i.e., the        total number of carbons in the molecule) straight or branched        chain alkyl or alkenyl disulphates, more preferably having the        formula:        wherein R is a straight or branched chain alkyl or alkenyl group        of chain length from about C₄ to about C₂₀;    -   (b) 1,4 disulphate compounds, preferably 1,4 C8-C22 straight or        branched chain alkyl or alkenyl disulphates, more preferably        having the formula:        wherein R is a straight or branched chain alkyl or alkenyl group        of chain length from about C₄ to about C₁₈; preferred R are        selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl,        hexadecyl, octadecyl, and mixtures thereof; and    -   (c) 1,5 disulphate compounds, preferably 1,5 C9-C23 straight or        branched chain alkyl or alkenyl disulphates, more preferably        having the formula:        wherein R is a straight or branched chain alkyl or alkenyl group        of chain length from about C₄ to about C₁₈.

It can be preferred that the dianionic surfactants of the invention arealkoxylated dianionic surfactants.

The alkoxylated dianionic surfactants of the invention comprise astructural skeleton of at least five carbon atoms, to which two anionicsubstituent groups spaced at least three atoms apart are attached. Atleast one of said anionic substituent groups is an alkoxy-linkedsulphate or sulphonate group. Said structural skeleton can for examplecomprise any of the groups consisting of alkyl, substituted alkyl,alkenyl, aryl, alkaryl, ether, ester, amine and amide groups. Preferredalkoxy moieties are ethoxy, propoxy, and combinations thereof.

The structural skeleton preferably comprises from 5 to 32, preferably 7to 28, most preferably 12 to 24 atoms. Preferably the structuralskeleton comprises only carbon-containing groups and more preferablycomprises only hydrocarbyl groups. Most preferably the structuralskeleton comprises only straight or branched chain alkyl groups.

The structural skeleton is preferably branched. Preferably at least 10%by weight of the structural skeleton is branched and the branches arepreferably from 1 to 5, more preferably from 1 to 3, most preferablyfrom 1 to 2 atoms in length (not including the sulphate or sulphonategroup attached to the branching).

A preferred alkoxylated dianionic surfactant has the formula

where R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl,ether, ester, amine or amide group of chain length C₁ to C₂₈, preferablyC₃ to C₂₄, most preferably C₈ to C₂₀, or hydrogen; A and B areindependently selected from, optionally substituted, alkyl and alkenylgroup of chain length C₁ to C₂₈, preferably C₁ to C₅, most preferably C₁or C₂, or a covalent bond; EO/PO are alkoxy moieties selected fromethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein n and m areindependently within the range of from about 0 to about 10, with atleast m or n being at least 1; A and B in total contain at least 2atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; Xand Y are anionic groups selected from the group consisting of sulphateand sulphonate, provided that at least one of X or Y is a sulfate group;and M is a cationic moiety, preferably a substituted or unsubstitutedammonium ion, or an alkali or alkaline earth metal ion.

The most preferred alkoxylated dianionic surfactant has the formula asabove where R is an alkyl group of chain length from C₁₀ to C₁₈, A and Bare independently C₁ or C₂, n and m are both 1, both X and Y are sulfategroups, and M is a potassium, ammonium, or a sodium ion.

Preferred alkoxylated dianionic surfactants herein include: ethoxylatedand/or propoxylated disulphate compounds, preferably C10-C24 straight orbranched chain alkyl or alkenyl ethoxylated and/or propoxylateddisulphates, more preferably having the formulae:

wherein R is a straight or branched chain alkyl or alkenyl group ofchain length from about C6 to about C₁₈; EO/PO are alkoxy moietiesselected from ethoxy, propoxy, and mixed ethoxy/propoxy groups; and nand m are independently within the range of from about 0 to about 10(preferably from about 0 to about 5), with at least m or n being 1.Anionic Carboxylate Surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxycarboxylates, the alkyl polyethoxy polycarboxylate surfactants and thesoaps (‘alkyl carboxyls’), especially certain secondary soaps asdescribed herein.

Suitable alkyl ethoxy carboxylates include those with the formulaRO(CH₂CH₂0)_(x) CH₂C00^(−M) ⁺ wherein R is a C₆ to C₈ alkyl group, xranges from 0 to 10, and the ethoxylate distribution is such that, on aweight basis, the amount of material where x is 0 is less than 20% and Mis a cation. Suitable alkyl polyethoxy polycarboxylate surfactantsinclude those having the formula RO—(CHR₁—CHR₂—O)—R₃ wherein R is a C₆to C₁₈ alkyl group, x is from 1 to 25, R₁ and R₂ are selected from thegroup consisting of hydrogen, methyl acid radical, succinic acidradical, hydroxysuccinic acid radical, and mixtures thereof, and R₃ isselected from the group consisting of hydrogen, substituted orunsubstituted hydrocarbon having between 1 and 8 carbon atoms, andmixtures thereof.

Suitable soap surfactants include the secondary soap surfactants whichcontain a carboxyl unit connected to a secondary carbon. Preferredsecondary soap surfactants for use herein are water-soluble membersselected from the group consisting of the water-soluble salts of2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoicacid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Certain soaps may also be included as suds suppressors.

Alkali Metal Sarcosinate Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates offormula R-CON (R¹) CH₂ COOM, wherein R is a C₅-C₁₇ linear or branchedalkyl or alkenyl group, R¹ is a C₁-C₄ alkyl group and M is an alkalimetal ion. Preferred examples are the myristyl and oleoyl methylsarcosinates in the form of their sodium salts.

Effervescence System

Any effervescence system known in the art can be used in the compositionof the invention. A preferred effervescence system comprises an acidsource, capable of reacting with an alkali source in the presence ofwater to produce a gas.

The acid source is preferably present at a level of from 0.5% to 35%,more preferably from 1.0% or even 2% to 20% or even form 4% to 20% byweight of the composition.

It may be preferred that the acid source or part thereof and the alkalisource or part thereof are comprised in an intimate mixture, for examplein the form of a compacted particle. The molecular ratio of the acidsource to the alkali source, is preferably from 50:1 to 1:50, morepreferably from 20:1 to 1:20 more preferably from 10:1 to 1:10, wherebywhen an intimate mixture of the acid source and the alkali source ispresent, this ratio is more preferably from 5:1 to 1:3, more preferablyfrom 3:1 to 1:2, more preferably from 2:1 to 1:2.

The acid source component may be any organic, mineral or inorganic acid,or a derivative thereof, or a mixture thereof. Preferably the acidsource component comprises an organic acid.

The acid compound is preferably substantially anhydrous ornon-hygroscopic and the acid is preferably water-soluble. It may bepreferred that the acid source is overdried.

Suitable acids source components include citric, malic, maleic, fumaric,aspartic, glutaric, tartaric succinic or adipic acid, monosodiumphosphate, boric acid, or derivative thereof. Citric acid, maleic ormalic acid are especially preferred.

Most preferably, the acid source provides acidic compounds which have anaverage particle size in the range of from about 75 microns to 1180microns, more preferably from 150 microns to about 710 microns,calculated by sieving a sample of the source of acidity on a series ofTyler sieves.

As discussed above, the effervescence system preferably comprises analkali source, however, for the purpose of the invention, it should beunderstood that the alkali source may be part of the effervescenceparticle or can be part of the cleaning composition comprising theparticle, or can be present in the washing liquor, whereto the particleor the cleaning composition is added.

Any alkali source which has the capacity to react with the acid sourceto produce a gas may be present in the particle, which may be any gasknown in the art, including nitrogen oxygen and carbondioxide gas.Preferred can be perhydrate bleaches, including perborate, and silicatematerial. The alkali source is preferably substantially anhydrous ornon-hydroscopic. It may be preferred that the alkali source isoverdried.

Preferably this gas is carbon dioxide, and therefore the alkali sourceis a preferably a source of carbonate, which can be any source ofcarbonate known in the art. In a preferred embodiment, the carbonatesource is a carbonate salt. Examples of preferred carbonates are thealkaline earth and alkali metal carbonates, including sodium orpotassium carbonate, bicarbonate and sesqui-carbonate and any mixturesthereof with ultra-fine calcium carbonate such as are disclosed inGerman Patent Application No. 2,321,001 published on Nov. 15, 1973.Alkali metal percarbonate salts are also suitable sources of carbonatespecies, which may be present combined with one or more other carbonatesources.

The carbonate and bicarbonate preferably have an amorphous structure.The carbonate and/or bicarbonates may be coated with coating materials.It can be preferered that the particles of carbonate and bicarbonate canhave a mean particle size of 75 microns or preferably 150 μm or greater,more preferably of 250 μm or greater, preferably 500 μm or greater. Itmay be preferred that the carbonate salt is such that fewer than 20% (byweight) of the particles have a particle size below 500 μ, calculated bysieving a sample of the carbonate or bicarbonate on a series of Tylersieves. Alternatively or in addition to the previous carbonate salt, itmay be preferred that the fewer than 60% or even 25% of the particleshave a particle size below 150 μm, whilst fewer than 5% has a particlesize of more than 1.18 mm, more preferably fewer than 20% have aparticle size of more than 212 μm, calculated by sieving a sample of thecarbonate or bicarbonate on a series of Tyler sieves.

Additional Ingredients

The compositions herein may contain additional detergent components. Theprecise nature of these additional components, and levels ofincorporation thereof will depend on the physical form of thecompositions comprising the builder component and the precise nature ofthe washing operation for which it is to be used.

Additional ingredients include additional builders, additionalsurfactants, bleach, enzymes, suds suppressors, lime soap, dispersants,soil suspension and anti-redeposition agents soil releasing agents,perfumes, brightners, photobleaching agents and additional corrosioninhibitors.

Water-Soluble or Partially Water-Soluble Builders

The composition preferably comprises one or more water-soluble orpartially water-soluble builders.

These include crystalline layered silicates an organic carboxylates orcarboxylic acids. The preferred crystalline layered silicate herein havethe general formulaNaMSi_(x)0_(2x+1).yH₂0wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is anumber from 0 to 20. Crystalline layered sodium silicates of this typeare disclosed in EP-A-0164514 and methods for their preparation aredisclosed in DE-A-3417649 and DE-A-3742043. For the purpose of thepresent invention, x in the general formula above has a value of 2, 3 or4 and is preferably 2. M is preferably H, K or Na or mixtures thereof,preferably Na. The most preferred material is α-Na₂Si₂0_(5, β)Na₂Si₂0₅or δNa₂Si₂0₅, or mixtures thereof, preferably being at least 75%—Na₂Si₂0₅, for example available from Clariant as NaSKS-6.

The crystalline layered silicate material, in particular of the formulaNa₂Si₂0₅ may optionally comprise other elements such as B, P, S, forexample obtained by processes as described in EP 578986-B.

The crystalline layered silicate may be in an intimate mixture withother materials, including one or more of surfactants of the surfactantsystem herein. Preferred other materials are other water-solublebuilders, including (poly) carboxylic acids and salts thereof, includingpolymeric compounds such as acrylic and/or maleic acid polymers,inorganic acids or salts, including carbonates and sulphates, or smalllevels of other silicate material, including amorphous silicate, metasilicates, and aluminosilicates, as described herein.

Suitable water-soluble builder compounds include the water solublemonomeric polycarboxylates, or their acid forms, homo or copolymericpolycarboxylic acids or their salts in which the polycarboxylic acidcomprises at least two carboxylic radicals separated from each other bynot more that two carbon atoms and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder can be monomeric oroligomeric in type although monomeric polycarboxylates are generallypreferred for reasons of cost and performance. In addition to thesewater-soluble builders, polymeric polycarboxyltes may be present,including homo and copolymers of maleic acid and acrylic acid and theirsalts.

Suitable carboxylates containing one carboxy group include the watersoluble salts of lactic acid, glycolic acid and ether derivativesthereof. Polycarboxylates containing two carboxy groups include thewater-soluble salts of succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronicacid and fumaric acid, as well as the ether carboxylates and thesulfinyl carboxylates.

Polycarboxylates containing three carboxy groups include, in particular,water-soluble citrates, aconitrates and citraconates as well assuccinate derivatives such as the carboxymethyloxysuccinates describedin British Patent No. 1,379,241, lactoxysuccinates described in BritishPatent No. 1,389,732, and aminosuccinates described in NetherlandsApplication 7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,439,000.Preferred polycarboxylates are hydroxycarboxylates containing up tothree carboxy groups per molecule, more particularly citrates.

Most preferred may be citric acid, malic acid, and fumaric acid, ortheir salts or mixtures thereof.

The parent acids of the monomeric or oligomeric polycarboxylatechelating agents or mixtures thereof with their salts, e.g. citric acidor citrate/citric acid mixtures, are also contemplated as useful buildercomponents.

Alkoxylated Nonionic Surfactant

Essentially any alkoxylated nonionic surfactants are suitable herein.The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes ofthe nonionic condensates of alkyl phenols, nonionic ethoxylatedalcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionicethoxylate/propoxylate condensates with propylene glycol, and thenonionic ethoxylate condensation products with propylene oxide/ethylenediamine adducts.

Nonionic Alkoxylated Alcohol Surfactant

The condensation products of aliphatic alcohols with from 1 to 25 molesof alkylene oxide, particularly ethylene oxide and/or propylene oxide,are suitable for use herein. The alkyl chain of the aliphatic alcoholcan either be straight or branched, primary or secondary, and generallycontains from 6 to 22 carbon atoms. Particularly preferred are thecondensation products of alcohols having an alkyl group containing from8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per moleof alcohol.

Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides suitable for use herein are those havingthe structural formula R²CONR¹Z wherein: R1 is H, C₁-C₄ hydrocarbyl,2-hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixturethereof, preferable C1-C4 alkyl, more preferably C₁ or C₂ alkyl, mostpreferably C₁ alkyl (i.e., methyl); and R₂ is a C₅-C₃₁ hydrocarbyl,preferably straight-chain C₅-C₁₉ alkyl or alkenyl, more preferablystraight-chain C₉-C₁₇ alkyl or alkenyl, most preferably straight-chainC₁₁-C₁₇ alkyl or alkenyl, or mixture thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl.

Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those having the formula:R⁶CON(R⁷)₂ wherein R⁶ is an alkyl group containing from 7 to 21,preferably from 9 to 17 carbon atoms and each R⁷ is selected from thegroup consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, and—(C₂H₄O)_(x)H, where x is in the range of from 1 to 3.

Nonionic Alkylpolysaccharide Surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Pat.No. 4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic groupcontaining from 6 to 30 carbon atoms and a polysaccharide, e.g., apolyglycoside, hydrophilic group containing from 1.3 to 10 saccharideunits.

Preferred alkylpolyglycosides have the formula:R²O(C_(n)H_(2n)O)t(glycosyl)_(x)wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived fromglucose.Amphoteric Surfactant

Suitable amphoteric surfactants for use herein include the amine oxidesurfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formulaR³(OR⁴)_(x)N⁰(R⁵)₂ wherein R³ is selected from an alkyl, hydroxyalkyl,acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containingfrom 8 to 26 carbon atoms; R⁴ is an alkylene or hydroxyalkylene groupcontaining from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to5, preferably from 0 to 3; and each R⁵ is an alkyl or hydroxyalkyl groupcontaining from 1 to 3, or a polyethylene oxide group containing from 1to 3 ethylene oxide groups. Preferred are C₁₀ -C₁₈ alkyl dimethylamineoxide, and C₁₀-C₁₈ acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2MConc. manufactured by Miranol, Inc., Dayton, N.J.

Zwitterionic Surfactant

Zwitterionic surfactants can also be incorporated into the detergentcompositions in accord with the invention. These surfactants can bebroadly described as derivatives of secondary and tertiary amines,derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Betaine and sultaine surfactants are exemplaryzwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formulaR(R′)₂N⁺R²COO⁻wherein R is a C₆-C₁₈ hydrocarbyl group, each R¹ istypically C₁-C₃ alkyl, and R² is a C₁--C₅ hydrocarbyl group. Preferredbetaines are C₁₂-C₁₈ dimethyl-ammonio hexanoate and the C₁₀-C₁₈acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complexbetaine surfactants are also suitable for use herein.

Cationic Surfactants

Suitable cationic surfactants to be used in the detergent herein includethe quaternary ammonium surfactants. Preferably the quaternary ammoniumsurfactant is a mono C₆-C₁₆, preferably C₆-C₁₀ N-alkyl or alkenylammonium surfactants wherein the remaining N positions are substitutedby methyl, hydroxyethyl or hydroxypropyl groups. Preferred are also themono-alkoxylated and bis-alkoxylated amine surfactants.

Another suitable group of cationic surfactants which can be used in thedetergent compositions or components thereof herein are cationic estersurfactants. The cationic ester surfactant is a, preferably waterdispersible, compound having surfactant properties comprising at leastone ester (i.e. —COO—) linkage and at least one cationically chargedgroup.

Suitable cationic ester surfactants, including choline estersurfactants, have for example been disclosed in U.S. Pat. Nos.4,228,042, 4,239,660 and 4,260,529.

In one preferred aspect the ester linkage and cationically charged groupare separated from each other in the surfactant molecule by a spacergroup consisting of a chain comprising at least three atoms (i.e. ofthree atoms chain length), preferably from three to eight atoms, morepreferably from three to five atoms, most preferably three atoms. Theatoms forming the spacer group chain are selected from the groupconsisting of carbon, nitrogen and oxygen atoms and any mixturesthereof, with the proviso that any nitrogen or oxygen atom in said chainconnects only with carbon atoms in the chain. Thus spacer groups having,for example, —O—O— (i.e. peroxide), —N—N—, and —N—O— linkages areexcluded, whilst spacer groups having, for example —CH₂—O—CH₂— and—CH₂—NH—CH₂— linkages are included. In a preferred aspect the spacergroup chain comprises only carbon atoms, most preferably the chain is ahydrocarbyl chain.

Cationic Monoalkoxylated Amine Surfactants

Highly preferred herein are cationic mono-alkoxylated amine surfactantpreferably of the general formula I:

wherein R¹ is an alkyl or alkenyl moiety containing from about 6 toabout 18 carbon atoms, preferably 6 to about 16 carbon atoms, mostpreferably from about 6 to about 14 carbon atoms; R² and R³ are eachindependently alkyl groups containing from one to about three carbonatoms, preferably methyl, most preferably both R² and R³ are methylgroups; R⁴ is selected from hydrogen (preferred), methyl and ethyl; X⁻is an anion such as chloride, bromide, methylsulfate, sulfate, or thelike, to provide electrical neutrality; A is a alkoxy group, especiallya ethoxy, propoxy or butoxy group; and p is from 0 to about 30,preferably 2 to about 15, most preferably 2 to about 8.

Preferably the ApR⁴ group in formula I has p=1 and is a hydroxyalkylgroup, having no greater than 6 carbon atoms whereby the —OH group isseparated from the quaternary ammonium nitrogen atom by no more than 3carbon atoms. Particularly preferred ApR⁴ groups are —CH₂CH₂OH,—CH₂CH₂CH₂OH, —CH₂CH(CH₃)OH and —CH(CH₃)CH₂OH, with —CH₂CH₂OH beingparticularly preferred. Preferred R¹ groups are linear alkyl groups.Linear R¹ groups having from 8 to 14 carbon atoms are preferred.

Another highly preferred cationic mono-alkoxylated amine surfactants foruse herein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, especiallyC₁₀-C₁₄ alkyl, preferably C₁₀ and C₁₂ alkyl, and X is any convenientanion to provide charge balance, preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein theethoxy (CH₂CH₂O) units (EO) are replaced by butoxy, isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

The levels of the cationic mono-alkoxylated amine surfactants used indetergent compositions of the invention is preferably from 0.1% to 20%,more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% byweight of the composition.

Cationic Bis-Alkoxylated Amine Surfactant

The cationic bis-alkoxylated amine surfactant preferably has the generalformula II:

wherein R¹ is an alkyl or alkenyl moiety containing from about 8 toabout 18 carbon atoms, preferably 10 to about 16 carbon atoms, mostpreferably from about 10 to about 14 carbon atoms; R² is an alkyl groupcontaining from one to three carbon atoms, preferably methyl; R³ and R⁴can vary independently and are selected from hydrogen (preferred),methyl and ethyl, X⁻ is an anion such as chloride, bromide,methylsulfate, sulfate, or the like, sufficient to provide electricalneutrality. A and A′ can vary independently and are each selected fromC₁-C₄ alkoxy, especially ethoxy, (i.e., —CH₂CH₂O—), propoxy, butoxy andmixtures thereof; p is from 1 to about 30, preferably 1 to about 4 and qis from 1 to about 30, preferably 1 to about 4, and most preferably bothp and q are 1.

Highly preferred cationic bis-alkoxylated amine surfactants for useherein are of the formula

wherein R¹ is C₁₀-C₁₈ hydrocarbyl and mixtures thereof, preferably C₁₀,C₁₂, C₁₄ alkyl and mixtures thereof. X is any convenient anion toprovide charge balance, preferably chloride. With reference to thegeneral cationic bis-alkoxylated amine structure noted above, since in apreferred compound R¹ is derived from (coconut) C₁₂-C₁₄ alkyl fractionfatty acids, R² is methyl and ApR³ and ApR⁴ are each monoethoxy.

Other cationic bis-alkoxylated amine surfactants useful herein includecompounds of the formula:

wherein R¹ is C₁₀-C₁₈ hydrocarbyl, preferably C₁₀-C₁₄ alkyl,independently p is 1 to about 3 and q is 1 to about 3, R² is C₁-C₃alkyl, preferably methyl, and X is an anion, especially chloride orbromide.

Other compounds of the foregoing type include those wherein the ethoxy(CH₂CH₂O) units (EO) are replaced by butoxy (Bu) isopropoxy[CH(CH₃)CH₂O] and [CH₂CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), ormixtures of EO and/or Pr and/or i-Pr units.

Perhydrate Bleaches

A highly preferred additional components of the compositions herein isan oxygen bleach, preferably comprising a hydrogen peroxide source and ableach precursor or activator.

A prferred source of hydrogen peroxide is a perhydrate bleach, such asmetal perborates, more preferably metal percarbonates, particularly thesodium salts. Perborate can be mono or tetra hydrated. Sodiumpercarbonate has the formula corresponding to 2Na₂CO₃.3H₂O₂, and isavailable commercially as a crystalline solid.

In particular the percarbonate salts are preferably coated. Suitablecoating agent are known in the art, and include silicates, magnesiumsalts and carbonates salts.

Potassium peroxymonopersulfate, sodium per is another optional inorganicperhydrate salt of use in the detergent compositions herein.

Organic Peroxyacid Bleaching System

A preferred feature of the composition herein is an organic peroxyacidbleaching system. In one preferred execution the bleaching systemcontains a hydrogen peroxide source and an organic peroxyacid bleachprecursor compound. The production of the organic peroxyacid occurs byan in situ reaction of the precursor with a source of hydrogen peroxide.Preferred sources of hydrogen peroxide include inorganic perhydratebleaches, such as the perborate bleach of the claimed invention. In analternative preferred execution a preformed organic peroxyacid isincorporated directly into the composition. Compositions containingmixtures of a hydrogen peroxide source and organic peroxyacid precursorin combination with a preformed organic peroxyacid are also envisaged.

Peroxyacid Bleach Precursor

Peroxyacid bleach precursors are compounds which react with hydrogenperoxide in a perhydrolysis reaction to produce a peroxyacid. Generallyperoxyacid bleach precursors may be represented as

where L is a leaving group and X is essentially any functionality, suchthat on perhydroloysis the structure of the peroxyacid produced is

Peroxyacid bleach precursor compounds are preferably incorporated at alevel of from 0.5% to 20% by weight, more preferably from 1% to 15% byweight, most preferably from 1.5% to 10% by weight of the detergentcompositions.

Suitable peroxyacid bleach precursor compounds typically contain one ormore N- or O-acyl groups, which precursors can be selected from a widerange of classes. Suitable classes include anhydrides, esters, imides,lactams and acylated derivatives of imidazoles and oximes. Examples ofuseful materials within these classes are disclosed in GB-A1586789.Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231and EP-A-0170386.

Leaving Groups

The leaving group, hereinafter L group, must be sufficiently reactivefor the perhydrolysis reaction to occur within the optimum time frame(e.g., a wash cycle). However, if L is too reactive, this activator willbe difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

and mixtures thereof, wherein R¹ is an alkyl, aryl, or alkaryl groupcontaining from 1 to 14 carbon atoms, R³ is an alkyl chain containingfrom 1 to 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizinggroup. Any of R¹, R³ and R⁴ may be substituted by essentially anyfunctional group including, for example alkyl, hydroxy, alkoxy, halogen,amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are —SO₃ ⁻M⁺, —CO₂ ⁻M⁺, —SO₄ ⁻M⁺, —N⁺(R³)₄X⁻ and O<—N(R³)₃ and most preferably —SO₃ ⁻M⁺ and —CO₂ ⁻M⁻ whereinR³ is an alkyl chain containing from 1 to 4 carbon atoms, M is a cationwhich provides solubility to the bleach activator and X is an anionwhich provides solubility to the bleach activator. Preferably, M is analkali metal, ammonium or substituted ammonium cation, with sodium andpotassium being most preferred, and X is a halide, hydroxide,methylsulfate or acetate anion.

Alkyl Percarboxylic Acid Bleach Precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids onperhydrolysis. Preferred precursors of this type provide peracetic acidon perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide typeinclude the N—N, N¹N¹ tetra acetylated alkylene diamines wherein thealkylene group contains from 1 to 6 carbon atoms, particularly thosecompounds in which the alkylene group contains 1, 2 and 6 carbon atoms.Tetraacetyl ethylene diamine (TAED) is particularly preferred. The TAEDis preferably not present in the agglomerated particle of the presentinvention, but preferably present in the detergent composition,comprising the particle.

Other preferred alkyl percarboxylic acid precursors include sodium3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodiumnonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate(ABS) and pentaacetyl glucose.

Amide Substituted Plkyl Peroxyacid Precursors

Amide substituted alkyl peroxyacid precursor compounds are suitableherein, including those of the following general formulae:

wherein R¹ is an alkyl group with from 1 to 14 carbon atoms, R² is analkylene group containing from 1 to 14 carbon atoms, and R⁵ is H or analkyl group containing 1 to 10 carbon atoms and L can be essentially anyleaving group. Amide substituted bleach activator compounds of this typeare described in EP-A-0170386.Perbenzoic Acid Precursor

Perbenzoic acid precursor compounds provide perbenzoic acid onperhydrolysis. Suitable O-acylated perbenzoic acid precursor compoundsinclude the substituted and unsubstituted benzoyl oxybenzene sulfonates,and the benzoylation products of sorbitol, glucose, and all saccharideswith benzoylating agents, and those of the imide type includingN-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoylsubstituted ureas. Suitable imidazole type perbenzoic acid precursorsinclude N-benzoyl imidazole and N-benzoyl benzimidazole. Other usefulN-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Preformed Organic Peroxyacid

The detergent composition may contain, in addition to, or as analternative to, an organic peroxyacid bleach precursor compound, apreformed organic peroxyacid, typically at a level of from 1% to 15% byweight, more preferably from 1% to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amidesubstituted compounds of the following general formulae:

wherein R¹ is an alkyl, aryl or alkaryl group with from 1 to 14 carbonatoms, R² is an alkylene, arylene, and alkarylene group containing from1 to 14 carbon atoms, and R⁵ is H or an alkyl, aryl, or alkaryl groupcontaining 1 to 10 carbon atoms. Amide substituted organic peroxyacidcompounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides,especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid anddiperoxyhexadecanedioc acid Mono- and diperazelaic acid, mono- anddiperbrassylic acid and N-phthaloylaminoperoxicaproic acid are alsosuitable herein.

Heavy Metal Ion Sequestrant

Heavy metal ion sequestrant are also useful additional ingredientsherein. By heavy metal ion sequestrant it is meant herein componentswhich act to sequester (chelate) heavy metal ions. These components mayalso have a limited calcium and magnesium chelation capacity, butpreferentially they show selectivity to binding heavy metal ions such asiron, manganese and copper. The are thus not considered builders for thepurpose of the invention.

Heavy metal ion sequestrants are generally present at a level of from0.005% to 10%, preferably from 0.1% to 5%, more preferably from 0.25% to7.5% and most preferably from 0.3% to 2% by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organicphosphonates, such as the amino alkylene poly (alkylene phosphonates),alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylenephosphonates.

Preferred among the above species are diethylene triamine penta(methylene phosphonate), ethylene diamine tri (methylene phosphonate)hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene1,1 diphosphonate, 1,1 hydroxyethane diphosphonic acid and 1,1hydroxyethane dimethylene phosphonic acid.

Other suitable heavy metal ion sequestrant for use herein includenitrilotriacetic acid and polyaminocarboxylic acids such asethylenediaminotetracetic acid, ethylenediamine disuccinic acid,ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinicacid or any salts thereof.

Other suitable heavy metal ion sequestrants for use herein areiminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid orglyceryl imino diacetic acid, described in EP-A-317,542 andEP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid andaspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acidsequestrants described in EP-A-516,102 are also suitable herein. Theβ-alanine-N,N′-diacetic acid, aspartic acid-N,N′-diacetic acid, asparticacid-N-monoacetic acid and iminodisuccinic acid sequestrants describedin EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331describes suitable sequestrants derived from collagen, keratin orcasein. EP-A-528,859 describes a suitable alkyl iminodiacetic acidsequestrant. Dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylicacid are also suitable. Glycinamide-N,N′-disuccinic acid (GADS),ethylenediamine-N-N′-diglutaric acid (EDDG) and2-hydroxypropylenediamine-N-N′-disuccinic acid (HPDDS) are alsosuitable.

Especially preferred are diethylenetriamine pentacetic acid,ethylenediamine-N,N′-disuccinic acid (EDDS) and 1,1 hydroxyethanediphosphonic acid or the alkali metal, alkaline earth metal, ammonium,or substituted ammonium salts thereof, or mixtures thereof.

Enzyme

Another preferred ingredient useful herein is one or more additionalenzymes.

Preferred additional enzymatic materials include the commerciallyavailable lipases, cutinases, amylases, neutral and alkaline proteases,cellulases, endolases, esterases, pectinases, lactases and peroxidasesconventionally incorporated into detergent compositions. Suitableenzymes are discussed in U.S. Pat. Nos. 3,519,570 and 3,533,139.

Organic Polymeric Compound

Organic polymeric compounds are preferred additional components of thecompositions herein.

By organic polymeric compound it is meant herein essentially anypolymeric organic compound commonly used as binder, dispersants, andanti-redeposition and soil suspension agents in detergent compositions,including any of the high molecular weight organic polymeric compoundsdescribed as clay flocculating agents herein, including quaternisedethoxylated (poly) amine clay-soil removal/anti-redeposition agent.

Organic polymeric compound is typically incorporated in the detergentcompositions of the invention at a level of from 0.01% to 30%,preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weightof the compositions.

Examples of organic polymeric compounds include the water solubleorganic homo- or co-polymeric polycarboxylic acids or their salts inwhich the polycarboxylic acid comprises at least two carboxyl radicalsseparated from each other by not more than two carbon atoms. Polymers ofthe latter type are disclosed in GB-A-1,596,756. Examples of such saltsare polyacrylates of MWt 1000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 2000 to100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived fromaspartic acid such as those disclosed in EP-A-305282, EP-A-305283 andEP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylicacid, polyaspartic acid and vinyl alcohol, particularly those having anaverage molecular weight of from 5,000 to 10,000, are also suitableherein.

Other organic polymeric compounds suitable for incorporation in thedetergent compositions herein include cellulose derivatives such asmethylcellulose, carboxymethylcellulose, hydroxypropylmethylcelluloseand hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols,particularly those of molecular weight 1000-10000, more particularly2000 to 8000 and most preferably about 4000.

Highly preferred polymeric components herein are cotton and non-cottonsoil release polymer according to U.S. Pat. No. 4,968,451, Scheibel etal., and U.S. Pat. No. 5,415,807, Gosselink et al., and in particularaccording to U.S. application Ser. No. 60/051517.

Another organic compound, which is a preferred claydispersant/anti-redeposition agent, for use herein, can be theethoxylated cationic monoamines and diamines of the formula:

an wherein X is a nonionic group selected from the group consisting ofH, C₁-C₄ alkyl or hydroxyalkyl ester or ether groups, and mixturesthereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene,propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), nis at least 16, with a typical range of from 20 to 35; for cationicdiamines (b=1), n is at least about 12 with a typical range of fromabout 12 to about 42.

Other dispersants/anti-redeposition agents for use herein are describedin EP-B-011965 and U.S. Pat. Nos. 4,659,802 and 4,664,848.

Suds Suppressing System

The detergent compositions of the invention, when formulated for use inmachine washing compositions, may comprise a suds suppressing systempresent at a level of from 0.01% to 15%, preferably from 0.02% to 10%,most preferably from 0.05% to 3% by weight of the composition.

Suitable suds suppressing systems for use herein may compriseessentially any known antifoam compound, including, for example siliconeantifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures ofcompounds which act such as to depress the foaming or sudsing producedby a solution of a detergent composition, particularly in the presenceof agitation of that solution.

Particularly preferred antifoam compounds for use herein are siliconeantifoam compounds defined herein as any antifoam compound including asilicone component. Such silicone antifoam compounds also typicallycontain a silica component. The term “silicone” as used herein, and ingeneral throughout the industry, encompasses a variety of relativelyhigh molecular weight polymers containing siloxane units and hydrocarbylgroup of various types. Preferred silicone antifoam compounds are thesiloxanes, particularly the polydimethylsiloxanes having trimethylsilylend blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acidsand soluble salts thereof. These materials are described in U.S. Pat.No. 2,954,347, issued Sep. 27, 1960 to Wayne St. John. Themonocarboxylic fatty acids, and salts thereof, for use as sudssuppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms,preferably 12 to 18 carbon atoms. Suitable salts include the alkalimetal salts such as sodium, potassium, and lithium salts, and ammoniumand alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecularweight fatty esters (e.g. fatty acid triglycerides), fatty acid estersof monovalent alcohols, aliphatic C₁₈--C₄₀ ketones (e.g. stearone)N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, bis stearic acid amideand monostearyl di-alkali metal (e.g. sodium, potassium, lithium)phosphates and phosphate esters.

A preferred suds suppressing system comprises:

-   -   (a) antifoam compound, preferably silicone antifoam compound,        most preferably a silicone antifoam compound comprising in        combination        -   (i) polydimethyl siloxane, at a level of from 50% to 99%,            preferably 75% to 95% by weight of the silicone antifoam            compound; and        -   (ii) silica, at a level of from 1% to 50%, preferably 5% to            25% by weight of the silicone/silica antifoam compound;        -   wherein said silica/silicone antifoam compound is            incorporated at a level of from 5% to 50%, preferably 10% to            40% by weight;    -   (b) a dispersant compound, most preferably comprising a silicone        glycol rake copolymer with a polyoxyalkylene content of 72-78%        and an ethylene oxide to propylene oxide ratio of from 1:0.9 to        1:1.1, at a level of from 0.5% to 10, preferably 1% to 10% by        weight; a particularly preferred silicone glycol rake copolymer        of this type is DCO544, commercially available from DOW Coming        under the tradename DCO544;    -   (c) an inert carrier fluid compound, most preferably comprising        a C₁₆-C₁₈ ethoxylated alcohol with a degree of ethoxylation of        from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%,        preferably 10% to 70%, by weight;

A highly preferred particulate suds suppressing system is described inEP-A-0210731 and comprises a silicone antifoam compound and an organiccarrier material having a melting point in the range 50° C. to 85° C.,wherein the organic carrier material comprises a monoester of glyceroland a fatty acid having a carbon chain containing from 12 to 20 carbonatoms. EP-A-0210721 discloses other preferred particulate sudssuppressing systems wherein the organic carrier material is a fatty acidor alcohol having a carbon chain containing from 12 to 20 carbon atoms,or a mixture thereof, with a melting point of from 45° C. to 80° C.

Other highly preferred suds suppressing systems comprisepolydimethylsiloxane or mixtures of silicone, such aspolydimethylsiloxane, aluminosilicate and polycarboxylic polymers, suchas copolymers of laic and acrylic acid.

Polymeric Dye Transfer Inhibiting Agents

The compositions herein may also comprise from 0.01% to 10%, preferablyfrom 0.05% to 0.5% by weight of polymeric dye transfer inhibitingagents.

The polymeric dye transfer inhibiting agents are preferably selectedfrom polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone andN-vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof,whereby these polymers can be cross-linked polymers.

Optical Brightener

The compositions herein also optionally contain from about 0.005% to 5%by weight of certain types of hydrophilic optical brighteners, as knownin the art.

Polymeric Soil Release Agent

Polymeric soil release agents, hereinafter “SRA”, can optionally beemployed in the present compositions. If utilized, SRA's will generallycomprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from0.2% to 3.0% by weight, of the compositions.

Preferred SRA's typically have hydrophilic segments to hydrophilize thesurface of hydrophobic fibers such as polyester and nylon, andhydrophobic segments to deposit upon hydrophobic fibers and remainadhered thereto through completion of washing and rinsing cycles,thereby serving as an anchor for the hydrophilic segments. This canenable stains occurring subsequent to treatment with the SRA to be moreeasily cleaned in later washing procedures.

Preferred SRA's include oligomeric terephthalate esters, typicallyprepared by processes involving at least onetransesterification/oligomerization, often with a metal catalyst such asa titanium(IV) alkoxide. Such esters may be made using additionalmonomers capable of being incorporated into the ester structure throughone, two, three, four or more positions, without, of course; forming adensely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linearester oligomer comprised of an oligomeric ester backbone ofterephthaloyl and oxyalkyleneoxy repeat units and allyl-derivedsulfonated terminal moieties covalently attached to the backbone, forexample as described in U.S. Pat No. 4,968,451, Nov. 6, 1990 to J. J.Scheibel and E. P. Gosselink. Such ester oligomers can be prepared by:(a) ethoxylating allyl alcohol; (b) reacting the product of (a) withdimethyl terephthalate (“DMT”) and 1,2-propylene glycol (“PG”) in atwo-stage transesterification/oligomerization procedure; and (c)reacting the product of (b) with sodium metabisulfite in water. OtherSRA's include the nonionic end-capped 1,2-propylenelpolyoxyethyleneterephthalate polyesters of U.S. Pat. No. 4,711,730, Dec. 8, 1987 toGosselink et al., for example those produced bytransesterification/oligomerization of poly(ethyleneglycol) methylether, DMT, PG and poly(ethyleneglycol) (“PEG”). Other examples of SRA'sinclude: the partly- and fully-anionic-end-capped oligomeric esters ofU.S. Pat. No. 4,721,580, Jan. 26, 1988 to Gosselink, such as oligomersfrom ethylene glycol (“EG”), PG, DMT andNa-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped blockpolyester oligomeric compounds of U.S. Pat. No. 4,702,857, Oct. 27, 1987to Gosselink, for example produced from DMT, methyl (Me)-capped PEG andEG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG andNa-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl,end-capped terephthalate esters of U.S. Pat. No. 4,877,896, Oct. 31,1989 to Maldonado, Gosselink et al., the latter being typical of SRA'suseful in both laundry and fabric conditioning products, an examplebeing an ester composition made from m-sulfobenzoic acid monosodiumsalt, PG and DMT, optionally but preferably further comprising addedPEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalateor propylene terephthalate with polyethylene oxide or polypropyleneoxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, May 25, 1976and U.S. Pat. No. 3,893,929 to Basadur, Jul. 8, 1975; cellulosicderivatives such as the hydroxyether cellulosic polymers available asMETHOCEL from Dow; the C₁-C₄ alkyl celluloses and C₄ hydroxyalkylcelluloses, see U.S. Pat. No. 4,000,093, Dec. 28, 1976 to Nicol, et al.;and the methyl cellulose ethers having an average degree of substitution(methyl) per anhydroglucose unit from about 1.6 to about 2.3 and asolution viscosity of from about 80 to about 120 centipoise measured at20° C. as a 2% aqueous solution. Such materials are available asMETOLOSE SM100 and METOLOSE SM200, which are the trade names of methylcellulose ethers manufactured by Shin-etsu Kagaku Kogyo K K.

Additional classes of SRA's include: (I) nonionic terephthalates usingdiisocyanate coupling agents to link polymeric ester structures, seeU.S. Pat. No. 4,201,824, Violland et al. and U.S. Pat. No. 4,240,918Lagasse et al.; and (II) SRA's with carboxylate terminal groups made byadding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With the proper selection of catalyst,the trimellitic anhydride forms linkages to the terminals of the polymerthrough an ester of the isolated carboxylic acid of trimelliticanhydride rather than by opening of the anhydride linkage. Eithernonionic or anionic SRA's may be used as starting materials as long asthey have hydroxyl terminal groups which may be esterified. See U.S.Pat. No. 4,525,524 Tung et al.. Other classes include: (III) anionicterephthalate-based SRA's of the urethane-linked variety, see U.S. Pat.No. 4,201,824, Violland et al.;

Other Optional Ingredients

Other optional ingredients suitable for inclusion in the compositions ofthe invention include perfumes, speckles, colours or dyes, filler salts,with sodium sulfate being a preferred filler salt.

Also, minor amounts (e.g., less than about 20% by weight) ofneutralizing agents, buffering agents, phase regulants, hydrotropes,enzyme stabilizing agents, polyacids, suds regulants, opacifiers,anti-oxidants, bactericides and dyes, such as those described in U.S.Pat. No. 4,285,841 to Barrat et al., issued Aug. 25, 1981 (hereinincorporated by (reference), can be present.

Highly preferred are encapsulated perfumes, preferably comprising astarch encapsulte.

In the compositions of the invention, it may be preferred that when dyesand/or perfumes are sprayed onto the another component, the componentdoes not comprise spray-on nonionic alkoxylated alcohol surfactant.

Form of the Compositions

The composition of the invention thereof can be made via a variety ofmethods involving the mixing of ingredients, including dry-mixing,compaction such as agglomerating, extrusion, tabletting, or spray-dryingof the various compounds comprised in the detergent component, ormixtures of these techniques, whereby the components herein also can bemade by for example compaction, including extrusion and agglomerating,or spray-drying.

The compositions herein can take a variety of physical solid formsincluding forms such as tablet, flake, pastille and bar, and preferablythe composition is in the form of granules or a tablet.

The compositions in accord with the present invention can also be usedin or in combination with bleach additive compositions, for examplecomprising chlorine bleach.

The compositions preferably have a density of more than 350 gr/liter,more preferably more than 450 gr/liter or even more than 570 gr/liter.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identificationshave the following meanings:

LAS Sodium linear C₁₁₋₁₃ alkyl benzene sulfonate LAS (I) Flakecontaining sodium linear C₁₁₋₁₃ alkyl benzene sulfonate (90%) and sodiumsulphate and moisture LAS(II) Potassium linear C₁₁₋₁₃ alkyl benzenesulfonate MES α-sulpho methylester of C₁₈ fatty acid TAS Sodium tallowalkyl sulfate CxyAS Sodium C_(1x)-C_(1y) alkyl sulfate C46SAS SodiumC₁₄-C₁₆ secondary (2,3) alkyl sulfate CxyEzS Sodium C_(1x)-C_(1y) alkylsulfate condensed with z moles of ethylene oxide CxyEz C_(1x)-C_(1y)predominantly linear primary alcohol condensed with an average of zmoles of ethylene oxide QAS R₂.N⁺(CH₃)₂(C₂H₄OH) with R₂ = C₁₂-C₁₄ QAS 1R₂.N⁺(CH₃)₂(C₂H₄OH) with R₂ = C₈-C₁₁ SADS Sodium C₁₄-C₂₂ alkyl disulfateof formula 2- (R).C₄ H₇.-1,4-(SO₄−)₂ where R = C₁₀-C₁₈ SADE2S SodiumC₁₄-C₂₂ alkyl disulfate of formula 2- (R).C₄ H₇.-1,4-(SO₄−)₂ where R =C₁₀-C₁₈, condensed with z moles of ethylene oxide APA C₈-C₁₀ aminopropyl dimethyl amine Soap Sodium linear alkyl carboxylate derived froman 80/20 mixture of tallow and coconut fatty acids STS Sodium toluenesulphonate CFAA C₁₂-C₁₄ (coco) alkyl N-methyl glucamide TFAA C₁₆-C₁₈alkyl N-methyl glucamide TPKFA C₁₆-C₁₈ topped whole cut fatty acids STPPAnhydrous sodium tripolyphosphate TSPP Tetrasodium pyrophosphate ZeoliteA Hydrated sodium aluminosilicate of formula Na₁₂(AlO₂SiO₂)₁₂.27H₂Ohaving a primary particle size in the range from 0.1 to 10 micrometers(weight expressed on an anhydrous basis) NaSKS-6 (I) Crystalline layeredsilicate of formula δ-Na₂Si₂O₅ of weight average particle size of 18microns and at least 90% by weight being of particle size of below 65.6microns. NaSKS-6 (II) Crystalline layered silicate of formula δ-Na₂Si₂O₅of weight average particle size of 18 microns and at least 90% by weightbeing of particle size of below 42.1 microns. Citric acid Anhydrouscitric acid Borate Sodium borate Carbonite Anydrous sodium carbonatewith a particle size between 200 μm and 900 μm Bicarbonate Anhydroussodium bicarbonate with a particle size distribution between 400 μm and1200 μm Silicate Amorphous sodium silicate (SiO₂:Na₂O = 2.0:1) SulfateAnhydrous sodium sulfate Mg sulfate Anhydrous magnesium sulfate CitrateTri-sodium citrate dihydrate of activity 86.4% with a particle sizedistribution between 425 μm and 850 μm MA/AA Copolymer of 1:4maleic/acrylic acid, average molecular weight about 70,000 MA/AA (1)Copolymer of 4:6 maleic/acrylic acid, average molecular weight about10,000 AA Sodium polyacrylate polymer of average molecular weight 4,500CMC Sodium carboxymethyl cellulose Cellulose ether Methyl celluloseether with a degree of polymerization of 650 available from Shin EtsuChemicals Protease Proteolytic enzyme, having 3.3% by weight of activeenzyme, sold by NOVO Industries A/S under the tradename SavinaseProtease I Proteolytic enzyme, having 4% by weight of active enzyme, asdescribed in WO 95/10591, sold by Genencor Int. Inc. AlcalaseProteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVOIndustries A/S Cellulase Cellulytic enzyme, having 0.23% by weight ofactive enzyme, sold by NOVO Industries A/S under the tradename CarezymeAmylase Amylolytic enzyme, having 1.6% by weight of active enzyme, soldby NOVO Industries A/S under the tradename Termamyl 120T Amylase IIAmylolytic enzyme, as disclosed in PCT/ US9703635 Lipase Lipolyticenzyme, having 2.0% by weight of active enzyme, sold by NOVO IndustriesA/S under the tradename Lipolase Lipase (1) Lipolytic enzyme, having2.0% by weight of active enzyme, sold by NOVO Industries A/S under thetradename Lipolase Ultra Endolase Endoglucanase enzyme, having 1.5% byweight of active enzyme, sold by NOVO Industries A/S PB4 Sodiumperborate tetrahydrate of nominal formula NaBO₂.3H₂O.H₂O₂ PB1 Anhydroussodium perborate bleach of nominal formula NaBO₂.H₂O₂ PercarbonateSodium percarbonate of nominal formula 2Na₂CO₃.3H₂O₂ DOBS Decanoyloxybenzene sulfonate in the form of the sodium salt DPDADiperoxydodecanedioc acid NOBS Nonanoyloxybenzene sulfonate in the formof the sodium salt NACA-OBS (6-nonamidocaproyl) oxybenzene sulfonateLOBS Dodecanoyloxybenzene sulfonate in the form of the sodium salt DOBSDecanoyloxybenzene sulfonate in the form of the sodium salt DOBADecanoyl oxybenzoic acid TAED Tetraacetylethylenediamine DTPA Diethylenetriamine pentaacetic acid DTPMP Diethylene triamine penta (methylenephosphonate), marketed by Monsanto under the Tradename Dequest 2060 EDDSEthylenediamine-N,N′-disuccinic acid, (S,S) isomer in the form of itssodium salt. Photoactivated bleach Sulfonated zinc phthlocyanine orsulfonated alumino phthlocyanine encapsulated in or carried by a solublepolymer Brightener 1 Disodium 4,4′-bis(2-sulphostyryl)biphenylBrightener 2 Disodium 4,4′-bis(4-anilino-6-morpholino-1.3.5-triazin-2-y1)amino) stilbene-2:2′-disulfonate HEDP 1,1-hydroxyethanediphosphonic acid PEGx Polyethylene glycol, with a molecular weight of x(typically 4,000) PEO Polyethylene oxide, with an average molecularweight of 50,000 TEPAE Tetraethylenepentaamine ethyoxylate PVI Polyvinylimidosole, with an average molecular weight of 20,000 PVPPolyvinylpyrolidone polymer, with an average molecular weight of 60,000PVNO Polyvinylpyridine N-oxide polymer, with an average molecular weightof 50,000 PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole,with an average molecular weight of 20,000 QEAbis((C₂H₅O)(C₂H₄O)_(n))(CH₃)-N⁺-C₆H₁₂-N⁺- (CH₃)bis((C₂H₅O)-(C₂H₄O))_(n), wherein n = from 20 to 30 SRP 1 Anionicallyend capped poly esters SRP 2 Diethoxylated poly (1,2 propyleneterephtalate) short block polymer PEI Polyethyleneimine with an averagemolecular weight of 1800 and an average ethoxylation degree of 7ethyleneoxy residues per nitrogen Silicone antifoam Polydimethylsiloxanefoam controller with siloxane-oxyalkylene copolymer as dispersing agentwith a ratio of said foam controller to said dispersing agent of 10:1 to100:1 Opacifier Water based monostyrene latex mixture, sold by BASFAktiengesellschaft under the tradename Lytron 621 Wax Paraffin wax

EXAMPLE I

A B C D E F G H I Blown powder LAS 5.0 8.0 3.0 5.0 5.0 10.0 — — — TAS —1.0 — — — — MBAS — — 5.0 5.0 — — — C₄₅AS — — 1.0 2.0 2.0 — — — C₄₅AE₃S —— 1.0 — — — QAS — — 1.0 1.0 — — — DTPA, HEDP and/ 0.3 0.3 0.5 0.3 — — —or EDDS MgSO4 0.5 0.5 0.1 — — — — Sodium citrate — — — 3.0 5.0 — — —Sodium carbonate 10.0 7.0 15.0 10.0 — — — Sodium sulphate 5.0 5.0 — —5.0 3.0 — — — Sodium silicate — — — — 2.0 — — — 1.6R Zeolite A 16.0 18.020.0 — — — — — — SKS-6 — — — 3.0 5.0 — — — — MA/AA or AA 1.0 2.0 11.0 —— 2.0 — — — PEG 4000 — 2.0 — 1.0 — 1.0 — — — QEA 1.0 — — — 1.0 — — — —Brightener 0.05 0.05 0.05 — 0.05 — — — — Silicone oil 0.01 0.01 0.01 — —0.01 — — — Agglomerate LAS — — — — — 2.0 — MBAS — — — — 2.0 — 1.0 C24AE₃— — — — — 1.0 0.5 Carbonate — — — 1.0 1.0 1.0 — Sodium citrate — — — — —— 5.0 CFAA — 2.0 — — 2.0 QAS — — — 1.0 — 1.0 1.0 QEA — — — 2.0 2.0 1.0 —SRP — — — 1.0 1.0 0.2 — Zeolite A — — — 10.0 26.0 15.0 16.0 Sodiumsilicate — — — — — — — PEG — — — — — — 4.0 — — Agglomerates SKS-6 6.08.0 — — 6.0 3.0 — 7.0 10.0 LAS 4.0 5.0 — — 5.0 3.0 — 10.0 12.0 Dry-addparticulate components Maleic 8.0 10.0 10.0 4.0 — 8.0 2.0 2.0 4.0acid/carbonate/ bicarbonate (40:20:40) QEA — — — 0.2 0.5 — — — — NACAOBS3.0 — — 1.5 — — — 2.5 — NOBS — 3.0 3.0 — — — — — 5.0 TAED 2.5 — — 1.52.5 6.5 — 1.5 — MBAS — — — 8.0 — — 8.0 — 4.0 LAS (I) 10.0 10.0 10.0 — —— 12.0 8.0 — Spray-on Brightener 0.2 0.2 0.3 0.1 0.2 0.1 — 0.6 — Dye — —— 0.3 0.05 0.1 — — — AE7 — — — — — 0.5 — 0.7 — Perfume — — — 0.8 — 0.5 —0.5 — Dry-add Citrate — — 20.0 4.0 — 5.0 15.0 — 5.0 Percarbonate 15.03.0 6.0 10.0 — — — 18.0 5.0 Perborate — — — — 6.0 18.0 — — — Photobleach0.02 0.02 0.02 0.1 0.05 — 0.3 — 0.03 Enzymes 1.3 0.3 0.5 0.5 0.8 2.0 0.50.16 0.2 (cellulase, amylase, protease, lipase) Zeolite A — — — 10.010.0 — — — — Carbonate 0.0 10.0 — — — 5.0 8.0 10.0 5.0 Perfume 0.6 0.50.5 — 0.3 0.5 0.2 0.1 0.6 (encapsulated) Suds suppressor 1.0 0.6 0.3 —0.10 0.5 1.0 0.3 1.2 Soap 0.5 0.2 0.3 3.0 0.5 — — 0.3 — Citric acid — —— 6.0 6.0 — — — 5.0 Dyed carboanate 0.5 0.5 1.0 2.0 — 0.5 0.5 0.5 1.0(blue, green) SKS-6 — — — 4.0 — — — 6.0 — Fillers up to 100%

EXAMPLE 2

The following are detergent formulations according to the presentinvention:

J K L M Blown Powder Zeolite A 12.0 20.0 — — Sodium sulfate — 5.0 2.0 —LAS — 10.0 3.0 — C45AS — 4.0 4.0 — QAS — — 1.5 — DTPA/HEDP/EDDS 0.4 0.40.4 — CMC 0.4 0.4 0.4 — Carbonate — — 3.0 AA or MA/AA 4.0 2.0 10.0 —Agglomerates QAS 1.0 — — — LAS 1.0 — 2.0 10.0 TAS — — — 1.0 Silicate 1.0— — 0.3 Zeolite A 8.0 — 8.0 3.0 Carbonate 8.0 — 4.0 3.0 AgglomerateNaSKS-6 15.0 12.0 — 10.0 LAS 8.0 13.0 — 8.0 AS 5.0 — — Spray On Perfume0.3 0.3 0.3 0.5 Brightener 0.01 0.01 0.01 0.01 C25E5 2.0 — 1.0 — Dryadditives LAS (I) — — 7.0 — QEA 1.0 0.5 0.5 0.5 Citrate — — 10.0 —Bicarbonate — 3.0 — Carbonate 8.0 15.0 10.0 NAC OBS 4.0 — — — TAED 2.0 —0.3 5.0 NOBS — 2.0 3.0 PC/PB1 14.0 3.0 3.0 18.0 PEG — — 0.9 0.5 Soap —0.5 — — Malic acid 7.0 — — — Zeolite A 2.0 — — — Polyethylene oxide of —— — — MW 5,000,000 Citric acid — — — 5.0 Protease 1.0 0.5 0.3 0.5 Lipase— 0.4 — — Amylase 0.6 0.6 0.6 Zeolite A — — 16.0 10.0 Cellulase 0.6 0.2— 0.3 SKS-6 — — 10.0 — SRP 0.1 0.1 0.1 0.1 CMC — 0.3 — 0.5 PVP — — 0.10.2 Silicone antifoam 0.5 1.5 1.0 0.3 Sodium sulfate 0.0 3.0 0.0 —Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre)800 600 700 850

EXAMPLE 3

The following are detergent formulations according to the presentinvention:

N O P R Agglomerate QAS 2.0 — 2.0 — MES — 2.0 — — LAS (II) 6.0 — — —C45AS 6.0 4.0 2.0 — MBAS16.5, 1.9 4.0 — — — Zeolite A — 6.0 8.0 8.0Carbonate 4.0 8.0 — 8.0 MA/AA 4.0 2.0 2.0 6.0 CMC 0.5 0.5 1.0 0.5 DTPMP0.4 0.4 — 0.5 Spray On C25E3 1.0 1.0 — — Perfume 0.5 0.5 0.5 0.5Agglomerate SKS-6 7.0 15.0 15.0 10.0 LAS 3.0 9.0 15.0 10.0 Zeolite 15.0— — — C45 AS — 3.0 — — Dry Adds LAS (I) — — — 15.0 EDDS/HEDP 0.5 0.3 0.50.8 Zeolite A 3.0 12.0 5.0 3.0 NaSKS 6 — — — 11.0 Citrate — 1.0 — —Citric acid 2.0 — 2.0 4.0 NAC OBS 4.1 — 5.0 4.0 TAED 0.8 2.0 — 2.0Percarbonate 20.0 20.0 15.0 17.0 SRP 1 0.3 0.3 — 0.3 Protease 1.4 1.41.0 0.5 Lipase 0.4 0.4 0.3 — Cellulase 0.6 0.6 0.5 0.5 Amylase 0.6 0.6 —0.3 QEA 1.0 — 1.0 1.0 Silicone antifoam 1.0 0.5 0.5 1.5 Brightener 1 0.20.2 — 6.2 Brightener 2 0.2 — 0.2 — Density (g/litre) 850 850 800 775

1. A detergent composition comprising an aluminosilicate builder and ananionic surfactant and comprising (n) components (i), n being at least2, whereby the level of aluminosilicate builder in said componentstogether is at least 5% by weight of the composition and the level ofthe anionic surfactant in said components together is at least 5% byweight of the composition, and whereby the degree of mixture (M) of theanionic surfactant and the aluminosilicate builder is from 0 to 0.7, MbeingΣ^(n) _(i=1)√(σ₁.ζ_(i)) σ is the fraction of the anionic surfactant ofthe composition comprised in component (i); ζ is the fraction of thealuminosilicate of the composition comprised in component (i) andwherein said aluminosilicate builder is in crystalline form and whereinsaid composition is phosphate-free, free of amorphous silicate, andsubstantially free of spray-on nonionic alkoxylated alcohol surfactantsand further wherein at least one component is made by a spray-dryingprocess and at least one component is made by an agglomeration processand wherein said component is a mixture of ingredients and eachcomponent represents a discrete part of the overall detergentcomposition.
 2. A detergent composition according to claim 1 wherein Mis from 0 to 0.65.
 3. A detergent composition according to claim 1,wherein the components are particles having a weight average particlesize of more than 150 microns.
 4. A detergent composition according toclaim 1, wherein said anionic surfactant comprises an alkyl sulphonatesurfactant or an alkylsulphate surfactant, or mixtures thereof.
 5. Adetergent composition according to claim 1 comprising at least 10% byweight of aluminosilicate builder, whereby part of the aluminosilicateis not comprised in the components.
 6. A detergent composition accordingto claim 1 wherein the components are free of sprayed-on nonionicalkoxylated alcohol surfactants.
 7. A composition according to claim 1wherein an effervescent system is present.
 8. A composition according toclaim 1 in granular form or in the form of a tablet.
 9. A compositionaccording to claim 1 comprising a hydrogen peroxide source and a bleachactivator.